电感耦合等离子体质谱法测定矿物渣中微量铀和钍

采用改进的微波消解程序处理矿物渣样品,用185Re作为内标同位素,以在线内标加入法补偿样品的基体干扰,提出了测定矿物渣中微量铀和钍的电感耦合等离子体质谱法.铀和钍的方法检出限分别为0.017,0.021 ng·g-1;铀和钍的平均加标回收率(n=6)分别为99.0%,101.3%;相对标准偏差(n=6)分别为4.02%和3.54%.两种标准物质中铀和钍的测定结果与标准值相符合.     

二溴对甲基偶氮磺褪色光度法测定铝合金中微量铬

在硝酸介质中,铬(Ⅵ)与二溴对甲基偶氮磺生成1:3物质的量比的稳定络合物,导致显色剂二溴对甲基偶氮磺吸光度降低,据此建立了褪色光度法测定铝合金中铬(Ⅵ)含量.对反应介质的种类和酸度、显色剂的用量、反应时间、共存离子的干扰等影响因素进行了试验并予以优化.在530 nm波长测定时,铬(Ⅵ)的质量浓度在0.032～0.48 mg·L-1范围内,反应体系吸光度的降低值△A与44(Ⅵ)浓度呈线性关系,表观摩尔吸光率为4.34×104L·mol-1.·cm-1.用于直接测定铝合金中微量铬的含量,测定值与标准值相符.相对标准偏差(n=8)小于2%.     

二硫代安替比林甲烷光度法测定铅冶炼废水中的微量砷

建立了利用二硫代安替比林甲烷光度法测定铅冶炼废水中微量砷的分析方法。在1.8mol·L^-1硫酸介质中,砷与二硫代安替比林甲烷显色剂发生灵敏的显色反应,最大吸收波长为331nm。考察了显色剂用量、显色反应时间、介质、酸度、不同价态砷对测定结果的影响。结果表明:使用4cm的比色皿,As^3+的质量浓度在0.04~0.6mg·L^-1内与其对应的吸光度之间呈线性关系,线性回归方程为y=1.063 x+0.001,相关系数为0.999 3,表观摩尔吸光系数为2.7×10^4L·mol^-1·cm^-1。按照标准加入法进行回收试验,测得回收率为97.0%~105%,相对标准偏差(n=5)为1.3%~2.6%,该方法用于测定铅冶炼废水中微量砷的结果满意。     

新显色剂二溴对甲基偶氮氯磺光度法测定铅的研究及应用

研究了铅与新显色剂二溴对甲基偶氮氯磺的显色反应,在 0.08mol~(-1)·L~(-1)的高氯酸介质中铅与二溴对甲基偶氮氯磺形成稳定的蓝色络合物,最大吸收波长为634nm.表观摩尔吸光系数ε=1.01×10~5L·mol~(-1)·cm~(-1),铅量在0～30μg/25ml内符合比耳定律.方法应用于铜合金中微量铅的测定,结果满意.     

1-偶氮苯-3-(3-硝基-5-氯-2-吡啶)-三氮烯的合成及其与汞的显色反应

合成了显色剂1-偶氮苯-3-(3-硝基-5-氯-2-吡啶)-三氮烯(ABNCPyT),并用元素分析法和红外光谱法对其分子结构作了鉴定.研究了ABNCPyT与汞的显色反应,在pH 10.5的Na2B4O7-NaOH缓冲溶液中和聚氧乙烯烷基酚(Triton X-100)表面活性剂存在下,试剂与汞(Ⅱ)生成4:1型红色配合物.配合物的最大吸收峰位于525 nm,表现摩尔吸光率为1.92×105L·mol-1·cm-1.汞(Ⅱ)质量浓度在600 靏稬-1以内符合比耳定律.用拟定方法测定废水中微量汞,所得结果与原子吸收光谱法的结果一致,测得其相对标准偏差(n=5)≤2.5%,方法的回收率在97.5%～103.0%.     

铬黑T分光光度法测定饮料中痕量镍

在pH 10.0的硼酸-氯化钾-氢氧化钠缓冲溶液中,显色剂铬黑T[1-(1-羟基-2-萘偶氮)-6-硝基-2-萘酚-4-磺酸钠]与镍(Ⅱ)形成稳定络合物。其最大吸收波长位于533nm处,表观摩尔吸光率为5.19×104L·mol-1·cm-1。镍(Ⅱ)的质量浓度在1.2mg·L-1范围内与吸光度呈线性关系。方法用于饮料样品中微量镍(Ⅱ)的测定,测定值与原子吸收光谱法测定结果一致,回收率在99.6%～100%之间,相对标准偏差(n=9)在1.4%～1.9%之间。     

1-(4-安替比林)-3-(3-硝基苯胺)三氮烯分光光度法测定镉(Ⅱ)

合成了一种新的显色剂三氮烯试剂1-(4-安替比林)-3-(3-硝基苯胺)三氮烯(ANTA),并研究了该显色剂与镉(Ⅱ)的显色反应。在Tween-80存在下及pH 10.2的硼砂-氢氧化钠缓冲溶液中,显色剂ANTA与镉(Ⅱ)形成2∶1的稳定络合物。其最大吸收波长位于508 nm波长处,表观摩尔吸光率为3.4×105L.mol-1.cm-1。镉(Ⅱ)的质量浓度在30.0~450μg.L-1范围内符合比耳定律,方法的检出限(3σ/k)为10.0μg.L-1。方法用于废水样品中微量镉(Ⅱ)的测定,测定结果与原子吸收光谱法相一致,平均回收率为103.5%,平均相对标准偏差(n=6)为4%。     

显色剂2-(1,3,4-三氮唑偶氮)-5-二乙氨基苯甲酸与镍的显色反应研究

研究了显色剂2-(1,3,4-三氮唑偶氮)-5-二乙氨基苯甲酸(TZDBA)与镍的显色反应,试剂与镍在pH 5.0的HAc-NaAc缓冲溶液中形成紫红色配合物,组成比为n(Ni2 )∶n(TZDBA)=1∶2,配合物表观摩尔吸光系数ε=3.82×104 L·mol-1·cm-1.镍质量浓度在0～0.8 mg/L范围内符合比尔定律.配合物形成后在强酸溶液中能稳定存在,有良好的选择性.方法不经分离直接测定铝合金和纯镁中的微量镍,测定结果与认定值相符.     

吸光光度法测定铜矿及金属铜中锌

微量锌的测定方法有极谱法、原子吸收分光光度法等,而吸光光度法因其仪器简单,灵敏度高还在不断发展.然而直接用于铜矿中微量锌的测定的吸光光度方法不多,而且大都使用萃取或离子交换分离技术.安替比林基重氮氨基偶氮苯(Cadion AP)是新合成试剂,曾用于人发中锌的吸光光度测定.本文将其用于铜矿及铜中微量锌测定,并以NaOH-NaCl-尿素体系的小体积沉淀分离法分离干扰元素,建立的方法简单适用.1 试验部分1.1 仪器与试剂722型光栅分光光度计pHS-2型酸度计锌标准溶液:1mg·ml~(-1)的贮备液显色剂:0.025%的CadionAP乙醇液B-R缓冲液:pH=11.7,将0.2mol·L~(-1)的氢氧化钠加到浓度分别为0.04mol·L~(-1)的硼酸、醋酸、     

2-(H-酸偶氮)-4,5-二硝基苯酚与钍的显色反应研究及其应用

研究了 2 (H 酸偶氮 ) 4 ,5二硝基苯酚 (HADNP)与钍的显色反应 ,在 pH 5 .5HOAc NaOAc缓冲介质中 ,溴化十六烷基吡啶 (CPB)存在下 ,HADNP与钍反应生成 2∶1稳定紫红色络合物 ,λmax=6 2 0nm ,ε =1.2 3× 10 5L·mol- 1·cm- 1。钍含量在 0～ 30 μg/2 5ml内符合比耳定律 ,方法用于环境水样品中钍含量的测定 ,结果满意。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.